Substituted acrylonitrile polymers



Patented se t. 18, 1945 SUBSTITUTED ACRYLONITBILE POLYMERS Albert M. Clifford, Stow, Ohio, minor to Win:-

foot Corporation, Akron, Ohio, a corporation of Delaware No Drawing. Application May 15, Serial No. 443,093

13 Claims. (CL 280-83) This invention relates to plastic masses preared from certain monomeric materials by poly..

merization or copolymerization thereof. More particularly, it relates to polymers of alpha substituted acrylonitriles either alone or interpolymerized with other monomers.

In the preparation of rubber-like masses from acrylonitriie and butadiene, it is found that the copolymers thus obtained are extremely tough and require special processing to render them capable of being handled in the manner customariiy employed in manipulating natural rubber. More workable synthetic rubbers of the acrylonitrile typeare desirable and it has now been found that such rubbers may be prepared by employing, in place of acrylonitriie, its alpha homologues in which the acrylonitrile-carries a -furyloxy or furfuryl-oxy or hydrocarbonoxy substituent. By the term "hydrocarbonoxy it is intended to include alkyloxy, aryloxy, cycloalkyi- -drous ethyl ether.

od of one hour and twenty minutes to a suspension of 147grams of CuCN and 300 cc. of anhy- The mixture was stirred and refluxed for another hour and forty minutes. The ether was distilled off, and the crude beta brom, alpha ethoxy propionitrile was distilled out The polymers may be prepared byany 01 the methods customarily employed in this type of manufacture, preferably by emulsion polymerization wherein the monomers are heated to a temperature ranging from -80 0., but'preferably between and 0., in an aqueous emulsion containing an emulsifier, such as Aquarex D or Duponol and an oxidant, such as sodium perborate or benzoyl peroxide. Other ingredients are also present in the emulsion and will be referred to hereinafter. (Aquarex D is a sodium salt mixture of sulfate mono-esters of a mixture of higher fatty alcohols consisting chiefly of the lauryl and myristyl derivatives. Duponol is a more concentrated form or. the same. Both products are manufactured by E. I. du Pont de Nemours and Company.) I v r The alpha hydrocarbonoxy acrylonitriles can be prepared by first treating an alpha, beta (ii-'- bromo dialiphatic ether with a cyanide to replace one atom of bromine with a nitrile' radical to form an alpha cyano beta bromo etheror beta bromo alpha hydrocarbonoxy propionitrile. This cyano ether may then be treated with a dehydrobronlinating agent, such as pyridine or quinciine to remove hydrogen bromide, thus producing the alpha hydrocarbonoxy acrylonitriie. For example, 378 grams of alpha, beta. dibromethyl ethyl ether were added with stirring over a periof the reaction mixture under reduced pressure. 178 grams of this crude product were mixed with 100 grams of pyridine and 2 grams of diphenyl para phenylene diamine (antioxidant). This mixture was heated for one and one-half to two hours on a steam bath in a flask fitted with a reflux condenser. At the end of this period the product was distilled out of the reaction mixture under reduced pressure and was washed with dilute hydrochloric acid to remove unreacted pyridine. The crude product was dried and fractionated under reduced pressure to produce the alpha ethoxy acrylonitrile. The new hydrocarbonoxy acrylonitrilesand the method of producing them are covered in Long application Serial #399,677, filed June 25, 1941, now Patent No. 2,326,373.

To illustrate the preparation of. the improved rubbers the following examples are given:

Example 1 To a olution of 10 cc. of 6% sodium lauryl sulfate in 4 ounce glass bombs was added 10 cc.

of a McIlvaine type phosphate-citrate bufi'er.'

There was also added 0.48 cc. of carbontetrachloride, 0.5 cc. of 5% sodium cyanide solution, 0.5 cc. of 10% acetaldehyde and 0.133 gram of sodium perborate. Sixteen grams of a mixture of monomers madeup of 9.6 grams of butadiene and 6.4

grams of the alpha substituted acrylonitrile, a /40 ratio, was then put into the emulsion, the

ibutadiene being added last, in the liquid state,

to the chilled mixture of the other ingredients. After closure the temperature of the bomb was maintained, during agitation, at 38 C. until polymerization to a desired yield was accomplished.

Monomer Hours m! Alpha ethoxy acryionitrlle Alpha methoxyacryionitl'ile Alpha n-butoxy acrylonitriie Percent Example 2 A polymerization on a larger scale was conducted of alpha ethoxy acrylonitrile. the batch being run in a live gallon glass-lined autoclave. Into this were placed one liter of water, 30 grams of sodium lauryl sulfate, 6.7 grams of sodium perborate, 24 grams of carbontetrachlorlde and 14.2 grams of disodium phosphate. To the emulsion thus made up were then added 371 grams of tained.

Example 3 The copolymer obtained in the foregoing example was then compounded as follows:

Grams copolymer 102.0 Sulfur 1.6 Stearic a 2.0 Benzothiazyl diethyl sulionamide 0.8 Carbon black 40.0

The cured rubber thus obtained was then subiected to physical testing and the. data obtained was tabulated as follows:

Tensile, Elong., Kg. Extrusion Cum lip/om. percent 300% plasticity In addition to the results obtained on the cured rubber from alpha ethoxy acrylonitrile+butadiene, the alpha methoizy acrylonitrile-i-butadlene and alpha n-butoxy acrylonitrile+butadiene rubbers of Example 1 were cured for 70 minutes at 260 F. and gave rubbers with tensiles of about 100 kg./cm.. All three of the copolymers were characterized by good plasticity and excellent processing qualities.

Other plastic materials which are embraced within the scope of the invention and fall within the class defined are those obtainable by mass polymerization of one or more individuals oi the alpha hydrocarbonoxy acrylonitrile type, such as alpha methoxy acrylonitrile. alpha ethoxy acrylonitrile, alpha propoxy acrylonitrile. alpha n-butoxy acrylonitrile. alpha isobutoxy acrylonitrile. alpha phenoxy acrylonitrile. alpha naphthoxy acrylonitrile, alpha benzyloxy acrylonitrile and alpha cyclohexyloxy acrylonitrile.

Any of the foregoing and other alpha hydrocarbonoxy acrylonitriles may be. copolymerized alpha alkyl acrylates, such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and the halogen substituted styrenes. such as the ortho, para and meta chloro styrenes and the ortho, para and meta bromo styrenes. Certain of the foregoing compounds may be aptly termed vinyl compounds or substituted vinyl compounds and these are especially useful in the formation of copolymersor interpolymers with the alkoxy acrylonitriles.

This application is a continuation-in-part of application Serial NO. 393,776, flied May 16, 1941.

While there have been described above certain preferred embodiments of the invention, it will be realized that the same is not limited thereto but that the ameliorating eflect of the presence of a hydrocarbonoxy substituent in the alpha position of acrylonitrile may be availed of in a wide variety of such substituents and particularly in connection with numerous other monomeric sub stances which may be interpolymerized with the substituted acrylonitrile to yield useful plastic masses. particularly those of rubber-like char- .acter. It will be apparent to those skilled in the art that various modifications and changes may be made without departing from the spirit of the invention or from the scope of the appended claims.

What I claim is:

1. Polymeric masses comprising a polymerized alpha hydrocarbonoxy-substltuted acrylonitrile.

2.Cop0lymers'c0mprising an alpha hydrocarbonoiw-substituted acrylonitrile interpolymerized with a butadiene.

' 3. Polymeric masses comprising at least one polymerized alpha hydrocarbonoxy-substituted acrylonitrile.

4. Polymeric masses comprising a polymerized alpha alkoxy substituted acrylonitrile.

5. Copolymers comprising an alpha hydrocarbonoxy-substituted acrylonitrile interpolymerized with a polymerizable -vinyl monomer.

6. Copolymers comprising an alpha alkoxy substituted acrylonitrile interpolymerized with a polymerizable vinyl monomer.

'I. Copolymers comprising an alpha alkoxy substituted acrylonitrile interpolymerized with a butadiene.

8. A copolymer comprising alpha methoxy acrylonitrile interpolymerized with butadiene-L3.

9. A copolymer comprising alpha ethoxy acrylonitrile'interpolymerlzed with butadine-1,3.

10. A copolymer comprising alpha butoxy acrylonitrile interpolymerized with butadiene-1,3.

ll. Polymeric masses comprising a polymerized alpha substituted acrylonitrile from the class consisting of alpha hydrocarbonoxy, furyl-oxy, and

. v furfuryl-oxy substituted acrylonitriles;

12. Copolymers comprising a polymerizable vinyl monomer interpolymerized with an alpha substituted acrylonitrile from the class consisting of the hydrocarbonoxy. furyl-oxy. and i'urfuryi-oxy substituted acrylonitriles.

13. A copolymer comprising butadiene-1,$ interpolymerized with an alpha substituted acrylonltrile from the class consisting of the hydrocarbonoxy, furyl-oxy, and furIuryl-oxy substituted acrylonitriles.

. ALBERT M. CLIFFORD. 

